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On the equilibrium of mono‐ and dinuclear Cu(II) dimethylglyoxime complexes and its exploitation for the simple preparation of Cu(I) salts [Cu(CH3CN)4]X (X = ClO4‐, BF4‐, OTf‐) 单核和双核铜(II)二甲基乙二醛肟络合物的平衡及其在简单制备铜(I)盐 [Cu(CH3CN)4]X (X = ClO4-, BF4-, OTf-) 中的应用
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-03-12 DOI: 10.1002/zaac.202300253
Raphael Immanuel Petrikat, Thomas Frick, Sabine Becker
{"title":"On the equilibrium of mono‐ and dinuclear Cu(II) dimethylglyoxime complexes and its exploitation for the simple preparation of Cu(I) salts [Cu(CH3CN)4]X (X = ClO4‐, BF4‐, OTf‐)","authors":"Raphael Immanuel Petrikat, Thomas Frick, Sabine Becker","doi":"10.1002/zaac.202300253","DOIUrl":"https://doi.org/10.1002/zaac.202300253","url":null,"abstract":"The reaction of Cu(OAc)2 with dimethylglyoxime (H2dmg) yields the mononuclear complex [Cu(Hdmg)2] (1), whereas the reaction of Cu(ClO4)2∙6H2O with H2dmg yields a dinuclear complex [Cu2(H2dmg)(Hdmg)(dmg)]ClO4 (2a). Systematic studies of the stoichiometric ratios of the reactants, the nature of the anion as well as pH value show that the pH value of the reaction solution/anion governs the nuclearity. I.e., basic anions and/or addition of a base yield 1. Once the product has formed in solution, it remains stable despite further changes of the pH value or addition of excess H2dmg. A conversion of one species into the other can only be achieved by simultaneous change of pH and addition of H2dmg. Accordingly, among sole addition of a base, 2a isomerizes but does not change its nuclearity. In contrast, if NaOtBu and H2dmg are added, 2a converts into 1. The same happens if the slightly basic salt Na2dmg is added to a solution of 2a. Furthermore, the formation of 2a can be exploited for the preparation of [Cu(CH3CN)4]X (X = ClO4‐, BF4‐, OTf‐) due to a recently reported cooperativity‐driven decomposition of 2a.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140125610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Gold(I) {2}‐Metallacoronates derived from a Catechol‐scaffolding Aroylbis(N,N‐diethylthiourea): Syntheses and Structures 源自邻苯二酚支架双(N,N-二乙基硫脲)的金(I) {2}-金属硼酸盐：合成与结构
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-02-23 DOI: 10.1002/zaac.202400012
Chien Thang Pham, Hung Huy Nguyen, Ulrich Abram, Thu Thuy Pham
{"title":"Gold(I) {2}‐Metallacoronates derived from a Catechol‐scaffolding Aroylbis(N,N‐diethylthiourea): Syntheses and Structures","authors":"Chien Thang Pham, Hung Huy Nguyen, Ulrich Abram, Thu Thuy Pham","doi":"10.1002/zaac.202400012","DOIUrl":"https://doi.org/10.1002/zaac.202400012","url":null,"abstract":"One‐pot reactions of a catechol‐scaffolding aroylbis(N,N‐diethylthiourea) H2Lcat and mixtures of lanthanide nitrates Ln(NO3)3 (Ln3+ = La3+, Nd3+ or Yb3+) or indium(III) chloride InCl3 and [Au(tht)Cl] in methanol in the presence of the supporting base Et3N result in gold(I) {2}‐metallacoronates. Depending on radii of the trivalent metal ions, the corresponding complexes are separated either in the neutral form with the composition {(NO3‐κ2‐O,O’)Ln [[EQUATION]] [Au2(Lcat)2]} in the cases of La3+ and Nd3+ or as the ‘ion‐pair’ {Yb [[EQUATION]] [Au2(Lcat)2]}+(NO3)‐ for the Yb(III) compound. The cationic complexes can be isolated in higher yields as the PF6‐ salts {M [[EQUATION]] [Au2(Lcat)2]}+(PF6)‐ (M3+ = Yb3+ or In3+) by treatment of reaction mixtures with (n‐Bu4N)(PF6).","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139948587","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Crystal Structure and Optical Characteristics of K2Nd2O(BO3)2 K2Nd2O(BO3)2 的晶体结构和光学特性
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-02-17 DOI: 10.1002/zaac.202400014
Jingcheng Feng, Jun Shen, Guochun Zhang
{"title":"Crystal Structure and Optical Characteristics of K2Nd2O(BO3)2","authors":"Jingcheng Feng, Jun Shen, Guochun Zhang","doi":"10.1002/zaac.202400014","DOIUrl":"https://doi.org/10.1002/zaac.202400014","url":null,"abstract":"A rare earth oxyborate crystal K2Nd2O(BO3)2 has been grown by means of high temperature solution method for the first time. It crystallizes in monoclinic P21/c (No. 14) space group, and the lattice parameters are a=11.318(6) Å, b=6.575(4) Å, c=10.689(6) Å, β=117.062(12)°, and Z=4. The absorption spectrum, emission spectrum, and fluorescence lifetime of K2Nd2O(BO3)2 have been evaluated, and the foundational spectral parameters have been analysed according to the Judd-Ofelt theory. The high concentration of activated ions (1.13×1022 ions/cm3), large absorption coefficient (87.63 cm-1), long fluorescence lifetime (91.2 μs), and large emission cross section (2.03×10-20 cm2) of K2Nd2O(BO3)2 suggest its potential applications of microchip lasers.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139928378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A Tb(III) complex based on 3−pyridylacetic showing luminescent detection for Fe3+ ion 一种基于 3-吡啶乙酸的锑(III)配合物，可对 Fe3+ 离子进行发光检测
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-02-16 DOI: 10.1002/zaac.202300246
Fang Liu, Ying-Bing Lu, Yu-Lin Zhou, Yu Lei, Bei-Bei Wang, Wei Yang, Wen-Tong Chen, Shui-Dong Zhu
{"title":"A Tb(III) complex based on 3−pyridylacetic showing luminescent detection for Fe3+ ion","authors":"Fang Liu, Ying-Bing Lu, Yu-Lin Zhou, Yu Lei, Bei-Bei Wang, Wei Yang, Wen-Tong Chen, Shui-Dong Zhu","doi":"10.1002/zaac.202300246","DOIUrl":"https://doi.org/10.1002/zaac.202300246","url":null,"abstract":"A new Tb(III) complex based on 3−pyridylacetic acid, [Tb(H(3−PAA)2)(NO3)2] (1, 3−PAA = 3−pyridylacetic ligand), has been triumphantly prepared and structurally characterized. Complex 1 is a 1D chained structure linked by carboxylate groups of the 3−PAA ligand, and its 2D supramolecular packing is controlled mainly by hydrogen-bonds. The compound exhibits outstanding thermal stability and excellent stability under CH3OH solutions. Moreover, compound 1 shows a strong solid-state green-emitting emission at room temperature, which demonstrates that the ligand can effectively sensitize the emission of the Tb(III) ion, and it can serve as a responsive sensing material for detecting the Fe3+ ion in CH3OH solutions.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139919140","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Reactions of Dichloroacetyl Fluoride in Superacidic Media 二氯乙酰氟在超酸性介质中的反应
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-02-15 DOI: 10.1002/zaac.202400013
Sebastian Steiner, Alexander Nitzer, Christoph Jessen, Andreas J. Kornath
{"title":"Reactions of Dichloroacetyl Fluoride in Superacidic Media","authors":"Sebastian Steiner, Alexander Nitzer, Christoph Jessen, Andreas J. Kornath","doi":"10.1002/zaac.202400013","DOIUrl":"https://doi.org/10.1002/zaac.202400013","url":null,"abstract":"Dichloroacetyl fluoride was investigated in the superacids HF/MF5 and DF/MF5 (M = As, Sb). The O-hemiprotonated species of dichloroacetyl fluoride is formed in the binary superacidic systems HF/MF5 and DF/MF5 (M = As, Sb) as hexafluoridoarsenates and hexafluoridoantimonates. With an excess of the strong Lewis acid SbF5 dichloroacetyl fluoride reacts under the formation of the oxonium salt [CCl2HCF2OX2][SbF6] in the superacidic system XF/SbF5 (X = H, D) after HF- or DF-addition, respectively. The colorless salts were characterized by low-temperature vibrational spectroscopy, NMR spectroscopy, and single-crystal X-ray diffraction. [CCl2HC(OH)F][(CCl2HCOF)2H][SbF6][Sb2F11] and [CCl2HCF2OH2][SbF6] crystallize in the monoclinic space groups P21/c and P21/m, respectively, with two formula units per unit cell each. The crystal structure of the oxonium salt shows strong O(-H)···F hydrogen bonds and strong F···F interactions. The experimental data are discussed together with quantum chemical calculations at the ωB97XD/aug-cc-pVTZ-level of theory.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139753015","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Front Cover: Dinucleating N-donor Ligands with 1,2-Diethynylbenzene Backbone for the Copper-Mediated Monooxygenation of Phenols (Z. Anorg. Allg. Chem. 4/2024) 封面：以 1,2-二乙炔基苯为骨架的二核化 N-供体配体用于铜介导的苯酚一氧化反应（Z. Anorg.）
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-02-15 DOI: 10.1002/zaac.202400015
Alexander Koch, Benjamin Herzigkeit, Küpra Yildiz, Christian Näther, Tobias A. Engesser, Felix Tuczek
{"title":"Front Cover: Dinucleating N-donor Ligands with 1,2-Diethynylbenzene Backbone for the Copper-Mediated Monooxygenation of Phenols (Z. Anorg. Allg. Chem. 4/2024)","authors":"Alexander Koch, Benjamin Herzigkeit, Küpra Yildiz, Christian Näther, Tobias A. Engesser, Felix Tuczek","doi":"10.1002/zaac.202400015","DOIUrl":"https://doi.org/10.1002/zaac.202400015","url":null,"abstract":"This cover picture shows an artistic representation of the conversion of monophenols to <i>ortho</i>-quinones mediated by dinuclear copper(I) complexes supported by tweezer-like ligands, thus serving as small-molecule model systems for the enzyme tyrosinase. We describe the first synthesis and characterization of the three different tweezer-like ligands Tw1-3 and their corresponding copper(I) complexes. In the picture, this class of ligands is exemplified by the pyrazole-terminated ligand Tw2. The hand holding the tweezers illustrates the ligand design that enables the corresponding complexes to hold dioxygen between their “tweezer arms”, mimicking the dinuclear active site of the enzyme and inducing the reaction with phenols. We would like to thank Philippa Kramer for the artistic design (DOI: 10.1002/zaac.202300237).","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139919157","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Amino Imidazolin-2-imine Ligands in Magnesium Complexes: Approaches Towards Low-Valent Mg(I) Species 镁配合物中的氨基咪唑啉-2-亚胺配体：实现低价镁（I）物种的途径
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-02-12 DOI: 10.1002/zaac.202300247
René Frank, Lars Denker, Mario Barthen
{"title":"Amino Imidazolin-2-imine Ligands in Magnesium Complexes: Approaches Towards Low-Valent Mg(I) Species","authors":"René Frank, Lars Denker, Mario Barthen","doi":"10.1002/zaac.202300247","DOIUrl":"https://doi.org/10.1002/zaac.202300247","url":null,"abstract":"Amino imidazoline-2-imines (AmIm) are a new class of chelating, monoanionic N,N´-donor ligands stronger than the analogous β-diketiminate ligands and give rise to five-membered metallacycles. The coordination chemistry of the monoanionic ligands 1,2-NHC=N−C6H4−NDipp− (i), cis-1,2-NHC=N−CMe=CMe−NDipp− (ii) was towards magnesium was investigated with the focus on the stabilization of low-valent magnesium(I) species, NHC = cyclo-C(NiPr2CMe)2, Dipp = 2,6-iPrC6H3. Both ligand systems (i) and (ii) form heteroleptic magnesium iodide species with were subjected to reduction. The complex [Mg(1,2-NHC=N−C6H4−NDipp)]2 was found to be insoluble, which prevented further purification. In contrast, the yield of the analogous complex [Mg(cis-1,2-NHC=N−CMe=CMe−NDipp)]2 was very low. As a significant side product the homoleptic complex [Mg(cis-1,2-NHC=N−CMe=CMe−NDipp)2] was identified.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139753018","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Reactivity of [ReOCl3(PPh3)2] towards substituted anilines ReOCl3(PPh3)2] 与取代苯胺的反应活性
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-02-06 DOI: 10.1002/zaac.202400007
Olivera Cvetković, Johannes Theiner, Mariusz J. Wolff, Kai Hultzsch
{"title":"Reactivity of [ReOCl3(PPh3)2] towards substituted anilines","authors":"Olivera Cvetković, Johannes Theiner, Mariusz J. Wolff, Kai Hultzsch","doi":"10.1002/zaac.202400007","DOIUrl":"https://doi.org/10.1002/zaac.202400007","url":null,"abstract":"The reactivity of [ReOCl3(PPh3)2] towards o-toluidine, m-toluidine, o-fluoroaniline, m-fluoroaniline, p-bromoaniline, p-chloroaniline and p-anisidine was examined and novel rhenium(V) imido complexes [Re(NC6H4R)Cl3(PPh3)2] (R = o-Me, m-Me, o-F, m-F, p-Cl, p-Br, p-OMe) were obtained. The resulting products were characterized by elemental analysis, electrospray ionization high-resolution mass spectrometry (ESI-HRMS), 1H, 13C{1H}, 19F{1H} and 31P{1H} NMR, FT-IR spectroscopy, and X-ray crystallography. For m-toluidine, m-fluroaniline and p-chloroaniline, rhenium(V) imido-amino mononuclear [Re(NC6H4R)Cl3(H2NC6H4R)(PPh3)] (R = m-F, p-Cl) complexes and binuclear [{Re(m-NC6H4Me)Cl2(m-H2NC6H4Me)(PPh3)}2O] complex were isolated as side products and characterized by X-ray crystallography. All six-coordinate rhenium(V) complexes display distorted octahedral coordination geometry.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139773232","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Well-defined Bis(imino)pyridine-Manganese(II) Complexes for Oxidation of Benzylic C-H Bonds 用于氧化苄基 C-H 键的定义明确的双(亚氨基)吡啶-锰(II)配合物
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-02-05 DOI: 10.1002/zaac.202300201
Chandrakanta Dash, Jyotirmoy Dey, Deepika Sahil, Ritu Raj Lakshkar, Om Prakash Joshi, Seema Yadav, Ajeet Singh, Sriparna Ray
{"title":"Well-defined Bis(imino)pyridine-Manganese(II) Complexes for Oxidation of Benzylic C-H Bonds","authors":"Chandrakanta Dash, Jyotirmoy Dey, Deepika Sahil, Ritu Raj Lakshkar, Om Prakash Joshi, Seema Yadav, Ajeet Singh, Sriparna Ray","doi":"10.1002/zaac.202300201","DOIUrl":"https://doi.org/10.1002/zaac.202300201","url":null,"abstract":"Two new manganese(II) complexes bearing bis(imino)pyridine pincer ligands have been synthesized. These manganese(II) complexes were characterized by UV, IR, elemental analysis studies, and X-ray crystallography. The X-ray crystal data of manganese complexes revealed distorted trigonalbipyramidal geometries around the manganese ion and neutral tridentate N∧N∧N coordination mode for bis(imino)pyridine (BIP) ligand. The catalytic properties of manganese(II) complexes were explored for the catalytic oxidation of the benzylic C-H bonds using TBHP as an oxidant. The corresponding carbonyl compounds have been produced in moderate to excellent yields.","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139753020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Die Geschichte der Chemie an der Ludwig‐Maximilians‐Universität München, mit zahlreichen Kurzbiographien von Professoren, die an der LMU gewirkt haben. 路德维希-马克西米利安-慕尼黑大学的化学史，并附有大量曾在慕尼黑大学工作的教授的简历。
Zeitschrift für anorganische und allgemeine Chemie Pub Date : 2024-02-02 DOI: 10.1002/zaac.202400009
{"title":"Die Geschichte der Chemie an der Ludwig‐Maximilians‐Universität München, mit zahlreichen Kurzbiographien von Professoren, die an der LMU gewirkt haben.","authors":"","doi":"10.1002/zaac.202400009","DOIUrl":"https://doi.org/10.1002/zaac.202400009","url":null,"abstract":"","PeriodicalId":23934,"journal":{"name":"Zeitschrift für anorganische und allgemeine Chemie","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139811320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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